• Title/Summary/Keyword: Cationic polymerization

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A study on the Coating Structure and Printability of Coated Paper (I) - Effect of Ionic Monomer on Paper-coating Latex Properties - (도공층 구조 및 도공지의 인쇄적성에 관한 연구 (I) - 이온성 단량체가 도공용 라텍스의 물성에 미치는 영향 -)

  • Lee, Yong-Kyu
    • Journal of the Korean Wood Science and Technology
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    • v.25 no.3
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    • pp.75-82
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    • 1997
  • To improve the quality of coated paper, the continuous research to the coating components and development of alternative latices is required. Recently, amphoteric latex is getting a great concern due to their changable properties of surface charge through controlling pH and some methods have been tried to prepare amphoteric latices. This study was carried out to synthesize amphoteric latex using seeding polymerization method with low concentration emulsifier. Styrene was used as a main monomer in addition to acrylonitrile for a hydrophilic comonomer. acrylic acid for a anionic comonomer and N,N-dimethylaminoethyl methacrylate for a cationic comonomer. Particle size and viscosity of latex were greatly affected by addition of acrylic acid and ammonium persulfate as an initiator. Negative charge of latex in alkali condition was changed to zero to positive charge in around pH 4.

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Polymerization of Tetrahydrofuran with New Transition Metal Catalyst and Its Mechanism: (p- Methylbenzyl)- o -cyanopyridinium Hexafluoroantimonate

  • 강준원;한양규
    • Bulletin of the Korean Chemical Society
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    • v.18 no.4
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    • pp.433-438
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    • 1997
  • (p-Methylbenzyl)-o-cyanopyridinium hexafluoroantimonate, a new catalyst, was synthesized by the reaction of o-cyanopyridine with α-bromo-p-xylene followed by exchange of counteranion with SbF6θ. We examined the effect of the catalyst on the bulk polymerization of tetrahydrofuran under various conditions. The catalytic activity was best in the presence of 1 : 1 of epichlorohydrin used as cocatalyst versus catalyst concentration. The resulting polymers had relatively low conversions in 1.0-40%. Their number average molecular weights were in the range of 800 to 5300. Propagation rate increased with increase in temperature according to an Arrhenius expression giving an activation energy of 62 KJ/mol. We also found catalyst proceeds via a cationic mechanism.

Preparation and characterization of prospective disulfide based electrode materials for lithium batteries

  • Ragupathy, Dhanusuraman;Gopalan, Anantha Iyengar;Lee, Kwang-Pill
    • Analytical Science and Technology
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    • v.21 no.1
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    • pp.25-33
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    • 2008
  • Organic disulfide compounds are having higher theoretical capacity than the conventional cathode material and are considered as the important storage material. Here, we are reporting the preparation of poly (2,2'-dithiodianiline) PDDA/multiwall carbon nanotubes, (MWCNTs) composites under different experimental conditions. Amine functionalized and unfunctionalized MWCNTs were independently used for the preparation of composites. Composites were prepared in the presence of cetyl trimethyl bromide (CTAB), a cationic surfactant, and also in the absence of CTAB. A physical mixture of PDTDA and MWCNTs was formed with unfunctionalized MWCNTs. Grafting of PDDA onto MWCNTs was performed by chemical oxidative polymerization of 2, 2'-dithiodianiline in the presence of amine functionalized MWCNTs. The composites of MWCNTs and PDTDA were characterized for structure, morphology and thermal properties through Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy, scanning electron microscopy and UV-visible spectroscopy. The composite materials prepared by this method are expected to find applications as electrode materials for lithium batteries.

Photo-induced Cationic Polymerization of Vinyl Ethers in the presence of Diphenyliodonium Salts (I) (디페닐요오드늄 염 존재하에서의 비닐 에테르의 광양이온중합 (I))

  • 권순홍;마석일
    • Proceedings of the Korean Fiber Society Conference
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    • 2002.04a
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    • pp.45-48
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    • 2002
  • 양이온 리빙 중합은 분자량 분포가 좁으며 분자량 및 말단기를 조절할 수 있고 블록공중합체의 합성이 용이하다는 장점이 있어 많은 연구들이 진행되어 왔다$^1$. 그러나 액체 또는 기체상의 개시제를 사용함으로 엄격히 건조된 상태의 중합계를 유지하기 위해 많은 주의를 기울여야 하는 단점이 있다. 본 연구실에서는 이러한 단점을 극복하기 위해 고체상인 요오드화 디페닐요오드늄(DPII)와 요오드화 아연을 광양이온 개시계로 이용한 이소부틸비닐에테르(IBVE)의 광양이온 리빙 중합을 보고한 바 있다. (중략)

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Photo-induced Living Cationic Polymerization of Isobutyl Vinyl Ether in the presence of Diphenyliodonium iodide and Zinc iodide(II) (Diphenlyiodonium Iodide와 Zinc Iodide 존재하의 비닐 에테르의 광양이온 리빙중합(II))

  • 권순홍;전현정;이연성;마석일
    • Proceedings of the Korean Fiber Society Conference
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    • 2001.10a
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    • pp.223-226
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    • 2001
  • 비닐에테르류의 비닐단량체는 ZnI$_2$ 존재하에서 HI와 같은 프로톤 산에 의해 양이온 리빙중합이 가능함이 보고된 바 있는데 이 때 프로톤산은 비닐에테르 단량체와 반응하여 adduct를 생성하고, ZnI$_2$는 adduct의 양이온중합 활성화제로 작용하는 것으로 알려져 있다. (중략)

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Synthesis of Characterization of Poly(alkylene oxide) Copolyols by Catioinc Ring Opening Polymerization and Their Azide Functionalized Copolyols (양이온 개환중합에 의한 폴리알킬렌 옥사이드 코폴리올의 합성과 아지드화 코폴리올의 특성 연구)

  • Lee, Jae-Myung;Seol, Yang-Ho;Kwon, Jung-Ok;Jin, Yong-Hyun;Noh, Si-Tae
    • Applied Chemistry for Engineering
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    • v.31 no.3
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    • pp.267-276
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    • 2020
  • Poly(epichlorohydrin) copolyol series (PECH copolyols) were synthesized via cationic ring-opening copolymerization (ROCP) of oxirane-based monomers and effects of reaction temperature, solvent type, and initiator were studied. As a comonomer, two types of alkylene oxides were used, and polymerization conditions were conducted both with diethylene glycol (DEG) as an initiator in methylene chloride (MC) solvent and tripropylene glycol (TPG) in toluene solvent. In order to induce the active monomer (AM) mechanism in the ring-opening copolymerization reaction, the monomer was injected by an incremental monomer addition (IMA) method using a syringe pump, and the polymerization was performed at -5 ℃. PECH copolyol, a synthesized ephichorohydrin (ECH)-based copolyol, was converted to glycidyl azide-based energy-containing copolyol (GAP copolyol) by azadizing the ECH unit through a substitution reaction. It was confirmed that the synthesized azide copolyol had little effects on changes of the solvent and the initiator. Also, the molecular weight increased 500 after the azide reaction, thereby the GAP copolyol was polymerized as designed. As the content of the comonomer increased, both the Tg and viscosity tended to decrease due to the influence of the alkyl chain length. It is possible to fundamentally prevent CH3N3 amount produced in the azide reaction process, and it is expected that a large-scale process could be achievable.

Theoretical Studies on the Cationic Polymerization Mechanism of Oxetanes(II) ($BF_3$촉매하의 옥세탄 공중합에 관한 분자 궤도론적 연구)

  • Park, Jeong Hwan;Cho, Sung Dong;Park, Seong Kyu;Cheun, Young Gu
    • Journal of the Korean Chemical Society
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    • v.40 no.1
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    • pp.11-19
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    • 1996
  • The cationic polymerization of energetic substituted oxetanes which have pendant energetic group such as azido and nitrato are investigated theoretically, using semiempirical HF/3-21G, MINDO/3, MNDO and AM1 method. The stereo- and electronic structure of binary molecular complex composed of energetic substituted oxetane and boron trifluoride can be explain by molecular orbital theory. The reactivity of propagation in the copolymerization of oxetanes can be presented by the positive charge on carbon(C2) atom of oxetane and energy level of the lowest unoccupied molecular orbital(LUMO) of propagating species of oxetanes. The reactivity ratios for copolymerization of oxetanes are a random copolymer-zation which is agree with MO calculated and experimental results. The relative equlibrium concentration of cyclic oxonium and open carbenium ions is found to be a major determinant of mechanism, owing to the rapid equilibrium of these cation forms and the expectation based on calculation that in the prepolymer propagation step, SN1 mechanism will be at least as fast as that for SN2 mechanism.

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Theoretical Studies on the Cationic Polymerization Mechanism of Oxiranes (산촉매하의 옥시란 공중합에 관한 분자궤도론적 연구)

  • Young-Gu Cheun
    • Journal of the Korean Chemical Society
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    • v.35 no.5
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    • pp.461-468
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    • 1991
  • The cationic polymerizations of substituted oxiranes which have pendant energetic groups such as azido, and nitrato, are investigated theoretically using the semiempirical MNDO, and $AM_1$ methods. The nucleophilicity and basicity of substituted oxiranes can be explained by the negative charge on oxygen atom of oxiranes. The reactivity of propagation in the polymerization of oxiranes can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxiranes. Ring opening of the complexed cyclic oxonium ion to the open chain carbenium ion is expected computational stability of the oxonium and carbenium ion by 30∼40 kcal/mol favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium and open carbenium ions will be a major determinant of mechanism. The chain growth $SN_1$, mechanism will be at least as fast as that for $SN_2$ mechanism.

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A Study Based on Molecular Orbital Theory of Polymerization of Oxolane High Explosives (Oxolane 고폭 화약류의 중합반응에 관한 분자 궤도론적 연구)

  • Kim, Joon-Tae
    • Applied Chemistry for Engineering
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    • v.21 no.3
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    • pp.278-283
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    • 2010
  • The cationic polymerization of oxolane high explosives which have pendant explosive groups such as azido, nitrato and hydrazino is investigated theoretically using the semiempirical MINDO/3, MNDO and AM1 methods. The nucleophilicity and basicity of oxolane high explosives can be explained by the negative charge on oxygen atom of oxolane. The reactivity of propagation in the polymerization of oxolane can be represented by the positive charge on carbon atom and the low LUMO energy of active species of oxolane. The reaction of the oxolane high explosives in oxonium ion form to the open chain carbenium ion form is expected by computational stability energy (17.950~30.197 kcal/mol) of the oxonium ion and carbenium ion favoring the carbenium ion. The relative equilibrium concentration of cyclic oxonium ion and carbenium ion is found to be a major determinant of mechanism, owing to the rapid equilibrium of these catoinic forms. Based on calculation, in the prepolymer propagation step, $S_N1$ mechanism will be at least as fast as that for $S_N2$ mechanism.